EP4379014A1 - Composition d'agent adhésif de type monocomposant et produit durci - Google Patents

Composition d'agent adhésif de type monocomposant et produit durci Download PDF

Info

Publication number
EP4379014A1
EP4379014A1 EP22849537.0A EP22849537A EP4379014A1 EP 4379014 A1 EP4379014 A1 EP 4379014A1 EP 22849537 A EP22849537 A EP 22849537A EP 4379014 A1 EP4379014 A1 EP 4379014A1
Authority
EP
European Patent Office
Prior art keywords
mass
polyoxyalkylene polymer
adhesive composition
component adhesive
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22849537.0A
Other languages
German (de)
English (en)
Inventor
Hitoshi Shimoma
Makito Nakamura
Chitoshi Suzuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of EP4379014A1 publication Critical patent/EP4379014A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers

Definitions

  • the present invention relates to a one-component adhesive composition and a cured product, and particularly to a urethane-based moisture-curable one-component adhesive composition that adheres different materials such as a resin and a metal, and a cured product obtained by curing the one-component adhesive composition.
  • steel plates are generally used for the interior and exterior articles, such as bodies, front doors, rear doors, back doors, front bumpers, rear bumpers, and rocker moldings, of automobiles, but in order to meet the demand for weight reduction, the number of cases increases where instead of steel plates, reinforced plastics such as carbon fiber-reinforced plastics and glass fiber-reinforced plastics, and various types of resin materials including polypropylene are used as the interior and exterior parts of automobiles. With this, the importance of techniques for adhering different materials such as a metal and a resin increases.
  • PTL1 discloses a two-component curable urethane-based composition including a main agent containing a urethane prepolymer, and a curing agent containing a polyether polyol having a predetermined molecular weight and an amine catalyst, and it is stated that the creep resistance is good.
  • PTL2 discloses a one-component curable composition in which a prepolymer obtained by reacting polypropylene glycol with a polyisocyanate compound is formed into a cured product.
  • the present inventors have studied diligently in order to solve the problem, and as a result, found that the problem can be solved by a one-component adhesive composition including an isocyanate group-terminated urethane prepolymer obtained by reacting a particular polyoxyalkylene polymer with a polyisocyanate compound. Thus, the present inventors have completed the present invention.
  • the present invention is as follows.
  • a one-component adhesive composition that is excellent in the heat resistance, moist heat resistance, and creep resistance at high temperature (90°C) of a cured product, can maintain adhesiveness even under high temperature, has a small temperature dependence of viscoelastic characteristics (storage modulus), and can stably exhibit adhesiveness in a wide temperature region, and a cured product obtained by curing the one-component adhesive composition.
  • XX to YY means “XX or more and YY or less”.
  • lower limit values and upper limit values described stepwise can each be independently combined. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", “the preferred lower limit value (10)” and “the more preferred upper limit value (60)” can also be combined into “ 10 to 60".
  • the upper limit values or lower limit values of the numerical value ranges may be replaced by values shown in Examples.
  • a "unit" constituting a polymer means an atomic group that a monomer forms by polymerization.
  • a "polyoxyalkylene polymer” means a polymer having a polyoxyalkylene chain.
  • a repeating unit based on an alkylene oxide is referred to as an "alkylene oxide unit”.
  • isocyanate group-terminated urethane prepolymer refers to a compound having an isocyanate group at at least part of the ends of the molecular chain and having a urethane bond in the molecular chain, obtained by reacting an organic compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound.
  • the inter-crosslinking molecular weight of a polyoxyalkylene polymer means a value obtained by dividing the number average molecular weight (Mn) of a polyoxyalkylene polymer by the average number of functional groups in the polyoxyalkylene polymer.
  • the average number of functional groups is the number of functional groups per molecule of the polyoxyalkylene polymer.
  • the present invention is a one-component adhesive composition including an isocyanate group-terminated urethane prepolymer obtained by reacting a particular polyoxyalkylene polymer with a polyisocyanate compound.
  • the one-component adhesive composition of the present invention is excellent in the heat resistance, moist heat resistance (the retention rate of breaking strength after moist heat is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more), and creep resistance at high temperature (90°C) of a cured product thereof, can maintain adhesiveness even under high temperature, has a small temperature dependence of viscoelastic characteristics (storage modulus), and can stably exhibit adhesiveness in a wide temperature region.
  • moist heat resistance the retention rate of breaking strength after moist heat is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more
  • creep resistance at high temperature (90°C) of a cured product thereof can maintain adhesiveness even under high temperature, has a small temperature dependence of viscoelastic characteristics (storage modulus), and can stably exhibit adhesiveness in a wide temperature region.
  • the polyoxyalkylene polymer constituting the isocyanate group-terminated urethane prepolymer has a functional group that can react with an isocyanate group, and has a number average molecular weight (hereinafter also described as "Mn") of 8000 or more, and in the polyoxyalkylene polymer, the content proportion of oxyethylene groups (ethylene oxide unit content; hereinafter also described as "EO unit content”) to the total amount of oxyalkylene groups is 5% by mass or more and 60% by mass or less.
  • Mn number average molecular weight
  • the EO unit content to the total amount of oxyalkylene groups in the polyoxyalkylene polymer is preferably 7% by mass or more, more preferably 9% by mass or more, and particularly preferably 11% by mass or more.
  • the EO unit content to the total amount of oxyalkylene groups in the polyoxyalkylene polymer is preferably 28% by mass or less, more preferably 25% by mass or less, and particularly preferably 22% by mass or less.
  • the polyoxyalkylene polymer When the EO unit content to the total amount of oxyalkylene groups in the polyoxyalkylene polymer is within the preferred range, the polyoxyalkylene polymer easily becomes amorphous and is therefore easily handled, and the heat resistance, moist heat resistance, and viscoelastic characteristics of a cured product of the obtained one-component adhesive composition easily become good.
  • the EO unit content to the total amount of oxyalkylene groups in the polyoxyalkylene polymer is calculated by obtaining the monomer composition of the oxyalkylene chain using 1 H-NMR.
  • the EO unit content to the total amount of oxyalkylene groups can be obtained from the area ratio of the signal of the methyl group in the propylene oxide unit to the signals of the methylene groups in the propylene oxide unit and in the EO unit.
  • the alkylene oxides used when the polyoxyalkylene polymer is synthesized are not particularly limited as long as they are selected so that the EO unit content to the total amount of oxyalkylene groups in the polyoxyalkylene polymer is 5% by mass or more and 60% by mass or less.
  • the combined use of preferably an alkylene oxide having 3 to 5 carbon atoms such as propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, or isobutylene oxide and ethylene oxide is preferred, and the combined use of propylene oxide and ethylene oxide is more preferred.
  • the arrangement of the units derived from the alkylene oxides may be a random, block, or tapered arrangement.
  • the polyoxyalkylene polymer may have a block form of propylene oxide units and a random form of EO units and propylene oxide units and may have a block form of EO units and a random form of EO units and propylene oxide units.
  • the polyoxyalkylene polymer may have a block form of propylene oxide units (PO block), a block form of EO units (EO block), and a PO block in this order (“PO block-EO block-PO block” structure) or may have an EO block, a PO block, and an EO block in this order (“EO block-PO block-EO block” structure).
  • PO block-EO block-PO block a block form of propylene oxide units
  • EO block-EO block-PO block PO block
  • EO block-EO block-EO block EO block-EO block
  • the polyoxyalkylene polymer has a block form of propylene oxide units, a random form of EO units and propylene oxide units, and a block form of EO units.
  • the molar ratio of the EO unit content to the content of the units of the alkylene oxide other than ethylene oxide is not particularly limited as long as the EO unit content to the total amount of oxyalkylene groups in the polyoxyalkylene polymer is 5% by mass or more and 60% by mass or less.
  • the hydrophilicity of the polyoxyalkylene polymer tends to improve.
  • the crystallinity of the polyoxyalkylene polymer tends to decrease.
  • the viscosity of the obtained one-component adhesive composition decreases easily, and the moist heat resistance of a cured product of the one-component adhesive composition easily becomes good.
  • the polyoxyalkylene polymer when an EO unit is at an end, a primary hydroxyl group is at an end, and therefore the reactivity with the polyisocyanate compound tends to be higher than when a propylene oxide unit is at an end.
  • the moist heat resistance and creep resistance at high temperature of a cured product of the one-component adhesive composition are better, and the adhesiveness is easily maintained even under high temperature.
  • the Mn of the polyoxyalkylene polymer is 8000 or more, preferably 8500 or more, more preferably 9000 or more, and particularly preferably 9500 or more.
  • the Mn of the polyoxyalkylene polymer is preferably 50000 or less, more preferably 40000 or less, further preferably 30000 or less, and particularly preferably 20000 or less.
  • the breaking strength, heat resistance, moist heat resistance, and creep resistance at high temperature (90°C) of a cured product of the obtained one-component adhesive composition are better.
  • the molecular weight distribution of the polyoxyalkylene polymer is not particularly limited but is preferably less than 1.20. By setting the molecular weight distribution of the polyoxyalkylene polymer at less than 1.20, the reactivity easily becomes good, the isocyanate group-terminated urethane prepolymer can be more efficiently produced, and the viscosity of the obtained isocyanate group-terminated urethane prepolymer decreases more easily.
  • the Mn and molecular weight distribution of the polyoxyalkylene polymer are values obtained by measurement by the method described below.
  • the molecular weight distribution is the value calculated from the Mw and Mn and is the ratio of Mw to Mn (hereinafter referred to as "Mw/Mn").
  • the degree of unsaturation of the polyoxyalkylene polymer is not particularly limited but is preferably 0.040 meq/g or less, more preferably 0.035 meq/g or less, and particularly preferably 0.030 meq/g or less.
  • the degree of unsaturation of the polyoxyalkylene polymer may be zero. When the degree of unsaturation of the polyoxyalkylene polymer is equal to or less than the upper limit value, the curability of the obtained isocyanate group-terminated urethane prepolymer is better.
  • the degree of unsaturation of the polyoxyalkylene polymer is a value measured according to the method of JIS K1557 3: 2007.
  • the polyoxyalkylene polymer has a functional group that can react with an isocyanate group.
  • the number of functional groups of the polyoxyalkylene polymer is preferably 3 or more, more preferably 3 to 10, further preferably 3 to 8, and particularly preferably 3 to 6.
  • the number of functional groups per molecule of the polyoxyalkylene polymer (hereinafter referred to as "the average number of functional groups") is preferably 2.5 or more, more preferably 2.8 or more, particularly preferably 3 or more and preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 3.
  • the breaking strength, heat resistance, moist heat resistance, and viscoelastic characteristics of a cured product of the obtained two-component adhesive composition easily become better.
  • Examples of the functional group of the polyoxyalkylene polymer include a hydroxyl group or an amino group.
  • the functional group of the polyoxyalkylene polymer is preferably a hydroxyl group, and a polyoxyalkylene polymer in which all functional groups are hydroxyl groups is more preferred.
  • the number of hydroxyl groups (hereinafter also referred to as "the number of hydroxyl groups") of the polyoxyalkylene polymer is preferably 3 or more, more preferably 3 to 10, further preferably 3 to 8, and particularly preferably 3 to 6.
  • the number of hydroxyl groups per molecule of the polyoxyalkylene polymer (hereinafter referred to as "the average number of hydroxyl groups”) is preferably 2.5 or more, more preferably 2.8 or more, further preferably 3.0 or more and preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 3.
  • the breaking strength, heat resistance, moist heat resistance, and viscoelastic characteristics of a cured product of the obtained one-component adhesive composition can be good.
  • the average number of functional groups as the whole of the polyoxyalkylene polymers is preferably 3 or more.
  • the average number of hydroxyl groups as the whole of the polyoxyalkylene polymers is preferably 3 or more.
  • the average number of hydroxyl groups per molecule of the polyoxyalkylene polymer can also be calculated by specifying the type(s) and molar ratio of the initiator(s) using 13 C-NMR (nuclear magnetic resonance).
  • 13 C-NMR nuclear magnetic resonance
  • the number of hydroxyl groups in one molecule of a polyoxyalkylene polymer matches the number of hydroxyl groups in one molecule of the initiator used when the polyoxyalkylene polymer is synthesized.
  • a polyoxyalkylene polymer is synthesized using, for example, glycerin, as an initiator, a polyoxyalkylene polymer in which the number of hydroxyl groups in one molecule is 3 is usually obtained.
  • a polyoxyalkylene polymer is synthesized using, for example, pentaerythritol, as an initiator, a polyoxyalkylene polymer in which the number of hydroxyl groups in one molecule is 4 is usually obtained.
  • a polyoxyalkylene polymer is synthesized using, for example, dipropylene glycol, as an initiator, a polyoxyalkylene polymer in which the number of hydroxyl groups in one molecule is 2 is usually obtained.
  • the inter-crosslinking molecular weight obtained by dividing the number average molecular weight (Mn) of the polyoxyalkylene polymer by the average number of functional groups is preferably 2000 or more, more preferably 2500 or more, particularly preferably 3000 or more and preferably 7000 or less, more preferably 6000 or less, and particularly preferably 5500 or less.
  • the hydroxyl value of the polyoxyalkylene polymer is not particularly limited but is preferably 2 mg KOH/g or more, more preferably 5 mg KOH/g or more, and particularly preferably 8 mg KOH/g or more and preferably 50 mg KOH/g or less, more preferably 45 mg KOH/g or less, and particularly preferably 40 mg KOH/g or less.
  • the hydroxyl value of the polyoxyalkylene polymer is equal to or less than the upper limit value, the viscoelastic characteristics of a cured product of the obtained one-component adhesive composition are better.
  • the hydroxyl value of the polyoxyalkylene polymer is a value measured and calculated according to the B method of JIS K 1557-1: 2007.
  • the polyoxyalkylene polymer may be used alone, and as long as the Mn thereof is 8000 or more, and the EO unit content to the total amount of oxyalkylene groups is 5% by mass or more and 60% by mass or less, two or more types of polyoxyalkylene polymers may be used in combination.
  • the EO unit content, Mn, and molecular weight distribution of each polyoxyalkylene polymer is preferably within the preferred range.
  • the method for producing the polyoxyalkylene polymer is not particularly limited but is preferably a method of subjecting alkylene oxides to ring-opening addition to an initiator having three or more hydroxyl groups in one molecule in the presence of a catalyst.
  • Examples of an initiator having three hydroxyl groups in one molecule include glycerin.
  • Examples of an initiator having four or more hydroxyl groups in one molecule include tetra- and higher-hydric polyhydric alcohols such as diglycerin, pentaerythritol, dipentaerythritol, and tripentaerythritol; and sugars such as glucose, sorbitol, dextrose, fructose, sucrose, and methyl glucoside, or derivatives thereof.
  • glycerin is preferred. Glycerin is inexpensively available, and the synthesis cost of the polyoxyalkylene polymer can be reduced.
  • the catalyst for subjecting the alkylene oxide to ring-opening addition polymerization to the initiator a conventionally known catalyst can be used.
  • the catalyst include alkali catalysts such as KOH, transition metal compound-porphyrin complex catalysts such as complexes obtained by reacting organoaluminum compounds with porphyrins, double metal cyanide complex catalysts (hereinafter also described as "DMC catalysts"), and catalysts including phosphazene compounds.
  • the polyoxyalkylene polymer is obtained using a DMC catalyst, it is preferred in that the molecular weight distribution of the obtained polyoxyalkylene polymer can be narrowed, and the polyoxyalkylene polymer having low viscosity is easily obtained.
  • DMC catalyst a conventionally known compound can be used, and also for the method for producing the polymer using a DMC catalyst, a known method can be adopted.
  • a known method can be adopted.
  • the compounds and production methods disclosed in WO 2003/062301 , WO 2004/067633 , JP 2004-269776 A , JP 2005-015786 A , WO 2013/065802 , and JP 2015-010162 A can be used.
  • the polyisocyanate compound used for being reacted with the polyoxyalkylene polymer to obtain the isocyanate group-terminated urethane prepolymer is an organic compound having two or more isocyanate groups in one molecule.
  • the number of isocyanate groups in one molecule is preferably 2 to 4.
  • One polyisocyanate compound can be used alone, or two or more polyisocyanate compounds can be used in combination.
  • polyisocyanate compound examples include linear or branched aliphatic diisocyanate compounds such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate;
  • linear or branched aliphatic diisocyanate compounds such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate
  • Examples of commercial products of the isocyanurate-modified products include DURANATE TPA-100 and DURANATE TKA-100 (manufactured by Asahi Kasei Corporation) and Coronate HX (manufactured by Tosoh Corporation).
  • Examples of commercial products of the biuret-modified products include DURANATE 24A-100 and DURANATE 22A-75P (manufactured by Asahi Kasei Corporation).
  • Examples of commercial products of the tri- and higher functional isocyanate group-terminated urethane prepolymers include Coronate L, Coronate L-55E, and Coronate L-45E (all are manufactured by Tosoh Corporation).
  • Examples of commercial products of the water-dispersible isocyanates include DURANATE WB40-100, DURANATE WB40-80D, DURANATE WT20-100, DURANATE WL70-100, DURANATE WE50-100, and DURANATE WR80-70P (manufactured by Asahi Kasei Corporation), and Aquanate 105, Aquanate 130, Aquanate 140, Aquanate 200, and Aquanate 210 (manufactured by Tosoh Corporation).
  • Examples of commercial products of the block isocyanates include SU-268A, NBP-211, MEIKANATE CX, MEIKANATE TP-10, and DM-6400 (all are manufactured by Meisei Chemical Works, Ltd.); WM44-L70G (manufactured by Asahi Kasei Corporation); Aqua BI200 and Aqua BI220 (all are manufactured by Baxenden chemicals); TAKELAC W and TAKELAC WPB (all are manufactured by Mitsui Chemicals, Inc.); BURNOCK (manufactured by DIC CORPORATION); and ELASTRON (manufactured by DKS Co. Ltd.).
  • the content of isocyanate groups in the polyisocyanate compound is preferably 20% by mass or more, more preferably 25% by mass or more, and particularly preferably 30% by mass or more and preferably 60% by mass or less, more preferably 55% by mass or less, and particularly preferably 50% by mass or less from the viewpoint of obtaining a one-component adhesive composition excellent in breaking strength, heat resistance, and creep resistance when cured.
  • polyisocyanate compound containing isocyanate groups in the preferred range aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds are preferred, and specifically, MDI (isocyanate group content 33.6% by mass), polymeric MDI (isocyanate group content 31.0% by mass), crude MDI (a mixture of MDI and triphenylmethane triisocyanate), and TDI (isocyanate group content 48.2% by mass) are preferred.
  • the isocyanate index representing 100 times the molar ratio of the isocyanate groups in the polyisocyanate compound to the hydroxyl groups in the polyoxyalkylene polymer (isocyanate group/hydroxyl group) is preferably 110 or more and 650 or less.
  • the isocyanate index is preferably 120 or more, more preferably 200 or more, and particularly preferably 300 or more and preferably 800 or less, more preferably 700 or less, and particularly preferably 680 or less.
  • the isocyanate index within the preferred range is preferred from the viewpoint that an isocyanate group-terminated urethane prepolymer having a moderate molecular chain length can be produced, and therefore the productivity improves more, and the breaking strength of a cured product of the one-component adhesive composition of the present invention is better.
  • the isocyanate index is the value obtained by centupling the ratio of the number of moles of the isocyanate groups of the polyisocyanate compound to the total number of moles of the hydroxyl groups of the polyoxyalkylene polymer.
  • the isocyanate group-terminated urethane prepolymer can be produced by reacting a polyoxyalkylene polymer with a polyisocyanate compound.
  • another polyol (a polyol other than a polyoxyalkylene polymer) as an optional component can also be used in combination.
  • another polyol include polyester polyols, poly(meth)acrylic polyols, polycarbonate polyols, polyolefin polyols, and castor oil-based polyols, and those described in [0016] to [0028] of JP 2020-37689 A can be used without particular limitation.
  • a polymer polyol in which a polymer having a unit based on a (meth)acrylate monomer is dispersed in a polyether polyol can also be used.
  • the polymer polyol may be a commercial product, and examples thereof include the "ULTIFLOW (registered trademark)” series and the “SHARPFLOW (registered trademark)” series (the above are manufactured by Sanyo Chemical Industries, Ltd.), and the “EXCENOL (registered trademark)” series (manufactured by AGC).
  • the content proportion of another polyol as an optional component is not particularly limited as long as the function of the isocyanate group-terminated urethane prepolymer constituting the one-component adhesive composition of the present invention is not inhibited.
  • the content proportion of another polyol as an optional component is preferably 30% by mass or less, more preferably 10% by mass or less, to the amount of the polyoxyalkylene polymer.
  • a catalyst for the production of the isocyanate group-terminated urethane prepolymer, a catalyst can be used as needed.
  • the catalyst examples include tertiary amine-based compounds; tin-based compounds; and non-tin-based compounds.
  • One catalyst can be used alone, or two or more catalysts can be used in combination.
  • tertiary amine-based compounds examples include triethylamine, triethylenediamine, and 1,8-diazabicyclo[5.4.0]-7-undecene (DBU).
  • DBU 1,8-diazabicyclo[5.4.0]-7-undecene
  • tin-based compounds examples include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
  • DBTDL dibutyltin dichloride
  • dibutyltin oxide dibutyltin dibromide
  • dibutyltin dimaleate dibutyltin dilaurate
  • DBTDL
  • non-tin-based compounds examples include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium-based compounds such as zirconium naphthenate.
  • titanium-based compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride
  • lead-based compounds such as lead oleate, lead 2-ethylhexan
  • the amount of the catalyst used when the catalyst is used is not particularly limited but is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and particularly preferably 0.003 parts by mass or more and preferably 1.0 part by mass or less, more preferably 0.2 parts by mass or less, and particularly preferably 0.05 parts by mass or less based on 100 parts by mass of the total of the polyoxyalkylene polymer and the polyisocyanate compound.
  • a solvent can be used as needed.
  • the solvent examples include ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; and aromatic hydrocarbons such as toluene and xylene.
  • ketones such as acetone and methyl ethyl ketone
  • esters such as ethyl acetate
  • aromatic hydrocarbons such as toluene and xylene.
  • One solvent can be used alone, or two or more solvents can be used in combination.
  • the amount of the solvent used when the solvent is used is not particularly limited but is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more and preferably 500 parts by mass or less, more preferably 450 parts by mass or less, and particularly preferably 400 parts by mass or less based on 100 parts by mass of the total of the polyoxyalkylene polymer and the polyisocyanate compound.
  • Examples of the method for producing the isocyanate group-terminated urethane prepolymer include the methods described below.
  • Production method 1 a method of charging a polyisocyanate compound, a polyoxyalkylene polymer, an optional catalyst, and an optional solvent together
  • Production method 2 a method of charging a polyoxyalkylene polymer, an optional catalyst, and an optional solvent, and adding a polyisocyanate compound dropwise thereto
  • the low molecular components in the raw materials are preferentially reacted, the molecular weight distribution can be more narrowed, and the reaction is easily controlled.
  • the reaction temperature is preferably 50°C or more, more preferably 60°C or more, and particularly preferably 65 or more and preferably less than 100°C, more preferably 95°C or less, and particularly preferably 80°C or less.
  • the reaction temperature is within the range, side reactions other than the urethane reaction are easily suppressed, and therefore the desired isocyanate group-terminated urethane prepolymer is easily obtained.
  • reaction terminating agent may be added to deactivate the catalyst.
  • examples of the reaction terminating agent include acetyl acetone. Two or more reaction terminating agents may be used in combination.
  • the Mn of the isocyanate group-terminated urethane prepolymer is not particularly limited but is preferably 8500 or more, more preferably 10000 or more, and particularly preferably 15000 or more and preferably 300000 or less, more preferably 250000 or less, and particularly preferably 200000 or less.
  • Mn is within the preferred range, an adhesive composition excellent in coating properties is obtained, and the viscosity during the synthesis can be adjusted.
  • the Mn of the isocyanate group-terminated urethane prepolymer can be obtained by GPC measurement by the same method as for the polyoxyalkylene polymer.
  • the inter-crosslinking molecular weight of the isocyanate group-terminated urethane prepolymer is not particularly limited but is preferably 2000 or more, more preferably 2500 or more, and particularly preferably 3000 or more and preferably 7000 or less, more preferably 6000 or less, and particularly preferably 5500 or less.
  • the inter-crosslinking molecular weight of the isocyanate group-terminated urethane prepolymer means the value obtained by dividing the number average molecular weight (Mn) of the polyoxyalkylene polymer that is a raw material of such a prepolymer by the average number of hydroxyl groups.
  • the EO unit content to the total amount of oxyalkylene groups in the isocyanate group-terminated urethane prepolymer is 5% by mass or more and 60% by mass or less, preferably 7% by mass or more, more preferably 9% by mass or more, and particularly preferably 11% by mass or more.
  • the EO unit content to the total amount of oxyalkylene groups in the isocyanate group-terminated urethane prepolymer is preferably 28% by mass or less, more preferably 25% by mass or less, and particularly preferably 22% by mass or less.
  • the EO unit content to the total amount of oxyalkylene groups in the isocyanate group-terminated urethane prepolymer is within the preferred range, the crystallinity of the obtained one-component adhesive composition is suppressed, and therefore the viscosity decreases easily, and the handling easily becomes easy. In addition, the moist heat resistance of a cured product is better.
  • the EO unit content to the total amount of oxyalkylene groups in the isocyanate group-terminated urethane prepolymer is calculated by obtaining the monomer composition of the oxyalkylene chain using 1 H-NMR.
  • the EO unit content to the total amount of oxyalkylene groups in the isocyanate group-terminated urethane prepolymer is the EO unit content to the total amount of oxyalkylene groups in the polyoxyalkylene polymer.
  • a known method can be applied to the method for producing the one-component adhesive composition of the present invention.
  • the order of introduction of the components is not particularly limited.
  • the one-component adhesive composition of the present invention it is possible to adopt a procedure in which the above-described particular polyoxyalkylene polymer is reacted with the above-described polyisocyanate compound to synthesize an isocyanate group-terminated urethane prepolymer first, and then an additive described later is blended into this isocyanate group-terminated urethane prepolymer, and the blend is uniformly stirred and mixed.
  • a catalyst can be used as needed.
  • the above-described catalysts are preferred.
  • the amount of the catalyst used is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and particularly preferably 0.05 parts by mass or more and preferably 1.0 part by mass or less, more preferably 0.9 parts by mass or less, and particularly preferably 0.8 parts by mass or less based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.
  • a reaction terminating agent is preferably added to deactivate the catalyst.
  • a solvent may be included in the one-component adhesive composition of the present invention as needed.
  • the above-described solvents are preferred.
  • the amount of the solvent used is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more and preferably 500 parts by mass or less, more preferably 450 parts by mass or less, and particularly preferably 400 parts by mass or less based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.
  • the content of the isocyanate group-terminated urethane prepolymer in the one-component adhesive composition of the present invention is preferably 50% by mass or more and 100% by mass or less, more preferably 55% by mass or more, and further preferably 60% by mass or more and more preferably less than 100% by mass, further preferably 99.5% by mass or less, and particularly preferably 95% by mass or less.
  • the content of the isocyanate group-terminated urethane prepolymer in the solids of the one-component adhesive composition of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more and may be 100% by mass.
  • the one-component adhesive composition of the present invention can include additives such as a hydrolysis inhibitor, an antioxidant, an ultraviolet absorbing agent, a light stabilizer, an antistatic agent, a leveling agent, and other optional components as needed, in a range that does not impair the effect of the present invention.
  • additives such as a hydrolysis inhibitor, an antioxidant, an ultraviolet absorbing agent, a light stabilizer, an antistatic agent, a leveling agent, and other optional components as needed, in a range that does not impair the effect of the present invention.
  • hydrolysis inhibitor examples include carbodiimide-based, isocyanate-based, oxazoline-based, and epoxy-based hydrolysis inhibitors.
  • One hydrolysis inhibitor can be used alone, or two or more hydrolysis inhibitors can be used in combination.
  • carbodiimide-based hydrolysis inhibitors are preferred from the viewpoint of a hydrolysis suppression effect.
  • the carbodiimide-based hydrolysis inhibitors are compounds having one or more carbodiimide groups in one molecule.
  • monocarbodiimide compounds include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, and naphthyl carbodiimide.
  • Polycarbodiimide compounds can be produced by subjecting a diisocyanate to a decarboxylation condensation reaction in the presence of a carbodiimidization catalyst.
  • diisocyanate examples include MDI, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, IPDI, 4,4'-dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate.
  • carbodiimidization catalyst examples include phospholene oxides such as 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof.
  • isocyanate-based hydrolysis inhibitors examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene
  • oxazoline-based hydrolysis inhibitors examples include 2,2'-o-phenylenebis(2-oxazoline), 2,2'-m-phenylenebis(2-oxazoline), 2,2'-p-phenylenebis(2-oxazoline), 2,2'-p-phenylenebis(4-methyl-2-oxazoline), 2,2'-m-phenylenebis(4-methyl-2-oxazoline), 2,2'-p-phenylenebis(4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis(4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline), 2,2'-hexamethylenebis(2-oxazoline), 2,2'-octamethylenebis(2-oxazoline), 2,2'-ethylenebis(4-methyl-2-oxazoline), and 2,2'-diphenylenebis(2-oxazoline).
  • epoxy-based hydrolytic agents examples include diglycidyl ethers of aliphatic diols such as 1,6-hexanediol, neopentyl glycol, and polyalkylene glycols; polyglycidyl ethers of aliphatic polyols such as sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol, and trimethylolpropane; polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol; diglycidyl esters or polyglycidyl esters of aliphatic or aromatic polyvalent carboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, and sebacic acid; diglycidyl ethers or polyglycidyl ethers of polyhydric phenol
  • the amount of the hydrolysis inhibitor added is not particularly limited but is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and particularly preferably 0.5 parts by mass or more and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and particularly preferably 3 parts by mass or less based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.
  • antioxidants examples include radical scavengers such as phenol-based compounds and amine-based compounds; and peroxide decomposers such as sulfur-based compounds and phosphorus-based compounds.
  • radical scavengers such as phenol-based compounds and amine-based compounds
  • peroxide decomposers such as sulfur-based compounds and phosphorus-based compounds.
  • One antioxidant can be used alone, or two or more antioxidants can be used in combination.
  • phenol-based compounds examples include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin- ⁇ -(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[ ⁇ -(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, benzenepropanoic acid, 3,5-bis(1,1-
  • Examples of the amine-based compounds include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, polycondensates of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidineethanol, N,N',N",N′′′-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, and polycondensates of dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine.
  • sulfur-based compounds examples include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate.
  • Examples of the phosphorus-based compounds include triphenyl phosphite, diphenyl isodecyl phosphite, 4,4'-butylidene-bis(3-methyl-6-tert-butylphenyl ditridecyl)phosphite, cyclic neopentanetetrayl bis(octadecyl phosphite), tris(nonylphenyl)phosphite, tris(monononylphenyl)phosphite, tris(dinonylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxid
  • the thermal deterioration of the isocyanate group-terminated urethane prepolymer can be prevented.
  • the amount of the antioxidant added is not particularly limited but is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.2 parts by mass or more and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.
  • one or more phenol-based compounds which are radical scavengers
  • Examples of the ultraviolet absorbing agent include benzophenone-based compounds, benzotriazole-based compounds, salicylic acid-based compounds, oxalic acid anilide-based compounds, cyanoacrylate-based compounds, and triazine-based compounds.
  • One ultraviolet absorbing agent can be used alone, or two or more ultraviolet absorbing agents can be used in combination.
  • the amount of the ultraviolet absorbing agent added is not particularly limited but is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.2 parts by mass or more and preferably 3 parts by mass or less, more preferably 2.5 parts by mass or less, and particularly preferably 2 parts by mass or less based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.
  • Examples of the light stabilizer include hindered amine-based compounds and hindered piperidine-based compounds.
  • One light stabilizer can be used alone, or two or more light stabilizers can be used in combination.
  • the amount of the light stabilizer added is not particularly limited but is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.2 parts by mass or more and preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, and particularly preferably 1 part by mass or less based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.
  • antistatic agent examples include inorganic salts, polyhydric alcohol compounds, ionic liquids, and surfactants.
  • One antistatic agent can be used alone, or two or more antistatic agents can be used in combination.
  • ionic liquids are preferred.
  • the "ionic liquid” is also referred to as a room temperature molten salt and is a salt having fluidity at 25°C.
  • inorganic salts examples include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, potassium nitrate, sodium nitrate, sodium carbonate, and sodium thiocyanate.
  • polyhydric alcohol compounds examples include propanediol, butanediol, hexanediol, polyethylene glycol, trimethylolpropane, and pentaerythritol.
  • ionic liquids examples include ionic liquids including imidazolium ions such as 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; ionic liquids including pyridinium ions such as 1-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexylpyridinium bis(trifluoromethylsulfonyl)imide, 1-octylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide
  • surfactants examples include nonionic low molecular surfactants such as glycerin fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, and fatty acid diethanolamides; anionic low molecular surfactants such as alkyl sulfonates, alkylbenzene sulfonates, and alkyl phosphates; cationic low molecular surfactants such as tetraalkylammonium salts and trialkylbenzylammonium salts; amphoteric low molecular surfactants such as alkyl betaines and alkylimidazolium betaines; nonionic polymeric surfactants such as a polyether ester amide type, an ethylene oxide-epichlorohydrin type, and a polyether ester type; anionic polymeric surfactants such as a polys,
  • the amount of the antistatic agent added is not particularly limited but is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and particularly preferably 0.05 parts by mass or more and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.
  • leveling agent examples include acrylic leveling agents, fluorine-based leveling agents, and silicone-based leveling agents.
  • One leveling agent can be used alone, or two or more leveling agents can be used in combination. Among these, acrylic leveling agents are preferred.
  • the amount of the leveling agent added is not particularly limited but is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and particularly preferably 0.1 parts by mass or more and preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, and particularly preferably 1 part by mass or less based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.
  • Examples of other optional components include catalysts, other resins other than isocyanate terminated urethane prepolymers, fillers (talc, calcium carbonate, titanium oxide, and the like), metal powders, colorants (pigments and the like), foil-like materials, softening agents, conductive agents, silane coupling agents, lubricants, corrosion inhibitors, heat resistance stabilizers, weather resistance stabilizers, polymerization inhibitors, and antifoaming agents.
  • the content proportion of oxyethylene groups to the total amount of oxyalkylene groups in the one-component adhesive composition of the present invention is not particularly limited but is preferably 10% by mass or more, more preferably 12% by mass or more, and particularly preferably 15% by mass or more and preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
  • the content proportion of oxyethylene groups to the total amount of oxyalkylene groups in the one-component adhesive composition of the present invention is within the preferred range, the adhesiveness to a high polarity base material improves more, and the moist heat resistance improves easily.
  • the EO unit content to the total amount of oxyalkylene groups in the one-component adhesive composition is calculated by obtaining the monomer composition of the oxyalkylene chain using 1 H-NMR.
  • the one-component adhesive composition of the present invention can be used for adhering glass, rubber, or a metal to a resin material or the like.
  • the resin material include polyolefins such as polypropylene, polyethylene, ethylene-propylene copolymers, and cycloolefin polymers; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polymethyl methacrylate; polycarbonates; polystyrene; acrylonitrile-styrene copolymers; polyvinyl chloride; polyacetates; acrylonitrile-butadienestyrene copolymers; and polyamides.
  • These resin materials may be subjected to surface treatment such as flame treatment, corona treatment, or ITRO treatment.
  • These resin materials may contain a filler such as talc, calcium carbonate, or alumina and may be reinforced with carbon fibers, glass fibers, or the like.
  • the one-component adhesive composition of the present invention can be used for the joining of the parts of not only an automobile body but various structures.
  • the one-component adhesive composition of the present invention can also be used, for example, as a paint, a waterproof material, a floor material, an elastomer, an artificial leather, and spandex, in addition to being used as an adhesive.
  • the cured product of the present invention is a cured product obtained by curing the one-component adhesive composition of the present invention and is, for example, a cured product cured by moisture.
  • moisture means "water vapor included in air”.
  • initiator A a triol (Mn: 1000) obtained by subjecting propylene oxide to ring-opening polymerization to glycerin was used (hereinafter referred to as an "initiator A").
  • the Mn, average number of hydroxyl groups, hydroxyl value, content of EO units, and inter-crosslinking molecular weight of the obtained polyoxyalkylene polymer (polyol A1) were measured as follows. The results are shown in Table 1.
  • the Mn of the polyoxyalkylene polymer is the polystyrene equivalent molecular weight obtained by measurement by gel permeation chromatography (GPC) under the following conditions using a calibration curve prepared using standard polystyrene samples whose molecular weight is known.
  • the hydroxyl value of the polyoxyalkylene polymer was calculated according to the B method of JIS K 1557-1: 2007.
  • the degree of unsaturation of a polyoxyalkylene polymer is a value measured according to the method of JIS K1557-3:2007.
  • the content of EO units to the total amount of oxyalkylene groups in the polyoxyalkylene polymer was calculated by obtaining the monomer composition of the oxyalkylene chain using 1 H-NMR.
  • the EO unit content can be obtained from the area ratio of the signal of the methyl group in the oxypropylene unit to the signals of the methylene groups in the oxypropylene unit and in the EO unit.
  • polyol A2 polyoxypropylene triol having EO units in a random form and in which the content of EO units was 19.8% by mass.
  • polyol A3 polyoxyalkylene polymer
  • polyol C1 polyoxyalkylene polymer
  • polyol C3 polyoxyalkylene polymer
  • polyol C5 polyoxypropylene triol having EO units in a block form and in which the content of EO units was 13.0% by mass.
  • polyol C6 polyoxyalkylene polymer
  • polyisocyanate compound Polymeric MDI: Millionate MR manufactured by Tosoh Corporation, isocyanate group content 31% by mass
  • polymeric MDI Millionate MR manufactured by Tosoh Corporation, isocyanate group content 31% by mass
  • 160.0 g of the polyol A1 was added, mixed at room temperature, then gradually heated, and reacted at an internal temperature of about 80°C for about 6 h.
  • the isocyanate index at the start of the reaction was 438, and the theoretical content of isocyanate groups including an end was 3.65% by mass.
  • Isocyanate index is a value obtained by centupling the ratio of the number of moles of the isocyanate groups of a polyisocyanate compound to the total number of moles of the hydroxyl groups of a polyoxyalkylene polymer used when an isocyanate group-terminated urethane prepolymer is produced.
  • Isocyanate group-terminated prepolymers (one-component adhesive compositions) were obtained by the same procedure as in Production Example 1 except that the types of the polyol and the polyisocyanate compound and the amounts of the polyol and the polyisocyanate compound blended (parts by mass) were changed as shown in Table 2.
  • the polyisocyanate compound used in Example 2 is meta-xylylene diisocyanate (TAKENATE 500 manufactured by Mitsui Chemicals, Inc., isocyanate group content 44.7% by mass).
  • the isocyanate index and the theoretical isocyanate group content for Production Examples 2 to 10 are shown in Table 2.
  • Creep resistance, breaking strength, a strength reaching rate, breaking strength after moist heat, storage moduli at -40°C and 130°C, and a modulus ratio were evaluated as follows. The evaluation results are shown together in Table 2.
  • a first non-treated fiber-reinforced unsaturated polyester resin (SMC) base material (3 mm) was coated with each of the isocyanate group-terminated prepolymers (one-component adhesive compositions) obtained in the Production Examples, and further a second SMC base material was superposed on and pressure-bonded to the coating isocyanate group-terminated urethane prepolymer so that the thickness of the isocyanate group-terminated urethane prepolymer was 250 ⁇ m.
  • SMC fiber-reinforced unsaturated polyester resin
  • a weight was mounted in a simplified holding power tester BE-502 (manufactured by TESTER SANGYO CO. LTD.) so as to obtain a load of 375.3 N [38.3 kgf] per 625 mm 2 (25 mm ⁇ 25 mm) of the adhesion area.
  • a creep test was performed at 90°C in the 180° shear direction, and the time (s) to the fall of the weight was measured.
  • a biaxially stretched polypropylene release film was coated with each of the isocyanate group-terminated prepolymers (one-component adhesive compositions) obtained in the Production Examples, so that the thickness was 200 ⁇ m, and allowed to stand under an atmosphere of 20°C and 60% RH (relative humidity) for 7 days for curing.
  • the release film was peeled to obtain a sheet-like adhesive cured product.
  • the tensile breaking strength (unit: MPa) was measured under the condition of a tensile rate of 300 mm/min using TENSILON (manufactured by A&D Company, Limited, product name: RTG-13 10).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP22849537.0A 2021-07-30 2022-07-27 Composition d'agent adhésif de type monocomposant et produit durci Pending EP4379014A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021125696 2021-07-30
PCT/JP2022/028931 WO2023008476A1 (fr) 2021-07-30 2022-07-27 Composition d'agent adhésif de type monocomposant et produit durci

Publications (1)

Publication Number Publication Date
EP4379014A1 true EP4379014A1 (fr) 2024-06-05

Family

ID=85087772

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22849537.0A Pending EP4379014A1 (fr) 2021-07-30 2022-07-27 Composition d'agent adhésif de type monocomposant et produit durci

Country Status (5)

Country Link
US (1) US20240199930A1 (fr)
EP (1) EP4379014A1 (fr)
JP (1) JPWO2023008476A1 (fr)
CN (1) CN117751173A (fr)
WO (1) WO2023008476A1 (fr)

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3315471B2 (ja) * 1992-04-27 2002-08-19 旭硝子株式会社 ポリウレタン系硬化性組成物
JPH06220152A (ja) * 1993-01-27 1994-08-09 Asahi Glass Co Ltd ポリウレタン系硬化性組成物
US5988616A (en) * 1997-06-26 1999-11-23 American Tool Companies, Inc. Full face pad
CA2302591C (fr) * 1997-09-26 2008-12-23 The Dow Chemical Company Elastomeres polyurethanne a temperature de service elevee
JP4623875B2 (ja) * 2001-07-09 2011-02-02 オート化学工業株式会社 湿気硬化型粘着性ポリウレタン系接着剤
JP4277686B2 (ja) 2002-01-22 2009-06-10 旭硝子株式会社 ポリエーテル類の連続製造方法
KR100990062B1 (ko) 2003-01-28 2010-10-29 아사히 가라스 가부시키가이샤 폴리에테르폴리올 조성물 및 그 용도
JP4277541B2 (ja) 2003-03-11 2009-06-10 旭硝子株式会社 ポリエーテルモノオールまたはポリエーテルポリオールの製造方法
JP4556496B2 (ja) 2003-06-04 2010-10-06 旭硝子株式会社 複合金属シアン化物錯体触媒、その製造方法およびその利用
JP2006145594A (ja) * 2004-11-16 2006-06-08 Canon Chemicals Inc 画像形成装置用部材
WO2011125951A1 (fr) 2010-04-02 2011-10-13 旭硝子株式会社 Mousse de polyuréthane flexible et procédé pour la produire
JP5648797B2 (ja) 2010-11-22 2015-01-07 旭硝子株式会社 ポリエーテルヒドロキシ化合物の製造方法
CN103890038A (zh) 2011-11-04 2014-06-25 旭硝子株式会社 聚醚的制造方法、预聚物的制造方法及改性硅氧烷聚合物的制造方法
JP6163918B2 (ja) 2013-06-28 2017-07-19 旭硝子株式会社 硬化性組成物
AU2018335768B2 (en) * 2017-09-22 2023-11-23 Henkel Ag & Co. Kgaa Solvent free liquid moisture curable polyurethane compositions with long open times and fast cure rates
KR102323585B1 (ko) 2018-09-03 2021-11-05 아라까와 가가꾸 고교 가부시끼가이샤 활성 에너지선 경화형 점착제 조성물, 경화물 및 점착시트

Also Published As

Publication number Publication date
JPWO2023008476A1 (fr) 2023-02-02
CN117751173A (zh) 2024-03-22
US20240199930A1 (en) 2024-06-20
WO2023008476A1 (fr) 2023-02-02

Similar Documents

Publication Publication Date Title
US10815330B2 (en) Thermolatently catalysed two-component system
WO2020230648A1 (fr) Solution contenant un prépolymère d'uréthane à terminaison hydroxyle, procédé de production pour solution contenant un prépolymère d'uréthane à terminaison hydroxyle, adhésif, feuille adhésive et procédé de production de feuille adhésive
JP2020512430A (ja) 低いブルーミング効果、及び良好な低温フレキシビリティーを示すポリウレタンを、ウレタン含有ポリマー性ヒドロキシル化合物に基づいて製造する方法。
EP3919579B1 (fr) Composition adhésive à base d'uréthane
US20030162930A1 (en) Terminal-blocked isocyanate prepolymer having oxadiazine ring, process for producing the same, and composition for surface-coating material
CN107109112B (zh) 经磷酸酯改性的丙烯酸多元醇
EP4379014A1 (fr) Composition d'agent adhésif de type monocomposant et produit durci
JP5132029B2 (ja) 塗料組成物
WO2015115291A1 (fr) Composition de polyisocyanate, résine polyuréthane durcissable de type en deux parties, matériau de revêtement, et adhésif
EP4379015A1 (fr) Composition adhésive de type bicomposant et objet durci
CN116472159B (zh) 二组分型涂布组合物
EP4169996A1 (fr) Composition adhésive d'uréthane
EP4249566A1 (fr) Composition adhésive à base d'uréthane
EP4269096A1 (fr) Dispersion aqueuse, composition d'adhésif, adhésif, matériau collant, et ruban adhésif
WO2023233962A1 (fr) Composition adhésive et article
JP7516842B2 (ja) 接着剤セット、並びに構造体及びその製造方法
JP7409217B2 (ja) 接着剤セット、並びに構造体及びその製造方法
EP3854857B1 (fr) Polymère organique, composition le contenant et son procédé de production
JP7415780B2 (ja) 接着剤セット、並びに構造体及びその製造方法
EP4349878A1 (fr) Polyuréthane à deux composants pour liaison de polycarbonate
JP7380677B2 (ja) 接着剤セット及び構造体の製造方法
WO2023204068A1 (fr) Composition d'adhésif, objet durci de cette composition d'adhésif, et procédé de fabrication de cette composition d'adhésif
JP2023145348A (ja) 粘着剤用水性組成物、粘着剤及びその製造方法、貼付材、並びに粘着テープ
JP2023145349A (ja) 粘着剤用水性組成物、粘着剤及びその製造方法、貼付材、並びに粘着テープ
JP2023132199A (ja) 構造用ポリウレタン接着剤

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240201

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR